WO2016194705A1 - Solid electrolyte composition, electrode sheet for all-solid-state secondary cell, all-solid-state secondary cell, and method for manufacturing electrode sheet for all-solid-state secondary cell and all-solid-state secondary cell - Google Patents

Abstract

A solid electrolyte composition containing a crystalline oxide-based inorganic solid electrolyte and a noncrystalline oxide-based inorganic solid electrolyte, wherein the ratio between the volume of the crystalline oxide-based inorganic solid electrolyte and the volume of the noncrystalline oxide-based inorganic solid electrolyte is 70-99.8:0.2-30.

Description

Solid electrolyte composition, electrode sheet for all-solid-state secondary battery, all-solid-state secondary battery, electrode sheet for all-solid-state secondary battery, and method for producing all-solid-state secondary battery

The present invention relates to a solid electrolyte composition, an electrode sheet for an all-solid secondary battery, an all-solid secondary battery, an electrode sheet for an all-solid secondary battery, and an all-solid secondary battery manufacturing method.

Electrolytic solutions have been used for lithium ion batteries. Attempts have been made to replace the electrolytic solution with a solid electrolyte to obtain an all-solid-state secondary battery in which the constituent materials are all solid. An advantage of the technology using an inorganic solid electrolyte is the reliability of the overall performance of the battery. For example, a flammable material such as a carbonate-based solvent is applied as a medium to an electrolytic solution used in a lithium ion secondary battery. In the secondary battery using such an electrolyte, various safety measures are taken. However, it cannot be said that there is no risk of problems during overcharging, and further measures are desired. An all-solid-state secondary battery that can make the electrolyte incombustible is positioned as a drastic solution.
A further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.

Because of the above advantages, development of an all-solid-state secondary battery as a next-generation lithium ion battery is being promoted (Non-patent Document 1). Development of technologies related to all-solid-state secondary batteries is also underway. For example, Patent Document 1 discloses a compound containing Li, B, and O and containing at least one element of C, Al, Si, Ga, Ge, In, and Sn, and crystalline lithium ion conductivity. A solid electrolyte containing the substance is described.

JP 2013-37992 A

The solid electrolyte described in Patent Document 1 can be used to improve lithium ion conductivity. However, the technique described in Patent Document 1 is premised on sintering a solid electrolyte and an active material in order to improve adhesion at a solid-solid interface. Therefore, when the technique described in Patent Document 1 is applied to the all-solid-state secondary battery, there is a problem that impurities are generated by sintering.

Therefore, the present invention provides a solid electrolyte composition capable of realizing good ionic conductivity without sintering in an all-solid-state secondary battery, an electrode sheet for an all-solid-state secondary battery using the same, and an all-solid-state secondary battery An object is to provide an electrode sheet for an all-solid-state secondary battery and a method for producing the all-solid-state secondary battery.

The present inventors diligently studied to solve the above-mentioned problems and completed the present invention.
All manufactured using a solid electrolyte composition containing a crystalline oxide-based inorganic solid electrolyte and an amorphous oxide-based inorganic solid electrolyte in a manner that can be performed under mild conditions without sintering. The solid secondary battery is presumed to contain an amorphous oxide-based inorganic solid electrolyte at the interface between solid particles. Therefore, the contact area between the solid particles increases through the amorphous oxide-based inorganic solid electrolyte, and the resistance at the interface is suppressed. As a result, the present inventors have found that the all-solid-state secondary battery produced using the solid electrolyte composition of the present invention can achieve good ionic conductivity without being sintered. The present invention has been made based on these findings.
That is, the above problem has been solved by the following means.

<1> A solid electrolyte composition comprising a crystalline oxide-based inorganic solid electrolyte and an amorphous oxide-based inorganic solid electrolyte, wherein the crystalline oxide-based inorganic solid electrolyte and the amorphous oxide-based inorganic solid A solid electrolyte composition having an electrolyte in a volume ratio of 70 to 99.8: 0.2 to 30.
<2> The solid electrolyte composition according to <1>, containing at least one binder having at least one functional group selected from the following functional group group [a].
Functional group [a]
Carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, hydroxy group, sulfanyl group, isocyanato group, oxetanyl group, epoxy group, dicarboxylic anhydride group, silyl group <3> Volume of crystalline oxide inorganic solid electrolyte The solid electrolyte according to <2>, wherein the ratio of the volume of the amorphous oxide-based inorganic solid electrolyte to the volume of the binder is 70 to 99.8: 0.1 to 29.9: 0.1 to 29.9 Composition.
<4> The resin according to <2> or <3>, wherein the resin constituting the binder is selected from the group consisting of a hydrocarbon resin, a fluorine-containing resin, an acrylic resin, polyurethane, polyamide, polyimide, polyether, polyester, and polycarbonate. Solid electrolyte composition.
<5> The solid electrolyte composition according to any one of <2> to <4>, wherein the functional group [a] is the following functional group [b].
Functional group [b]
<2> to <5>, wherein the resin constituting the carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, hydroxy group, dicarboxylic anhydride group, silyl group <6> binder is an acrylic resin or polyurethane The solid electrolyte composition as described in any one.
<7> The solid electrolyte composition according to any one of <2> to <6>, wherein the binder is particles having an average particle diameter of 0.01 μm to 10 μm.
<8> The solid electrolyte composition according to any one of <1> to <7>, wherein the amorphous oxide-based inorganic solid electrolyte includes a compound represented by the following formula (I).
Li _{xc Byc} M ^cc _{zc Onc} formula (I)
In the formula (I), M ^cc is at least one selected from the group consisting of C, S, Al, Si, P, Ga, Ge, In and Sn, and xc, yc, zc and nc have a composition ratio. 0 <xc ≦ 5, 0 <yc ≦ 1, 0 ≦ zc ≦ 1, and 0 <nc ≦ 6.
<9> The solid electrolyte composition according to any one of <1> to <8>, wherein the crystalline oxide-based inorganic solid electrolyte is selected from compounds of the following formula:
・ Li _xa La _ya TiO ₃
xa = 0.3 to 0.7, ya = 0.3 to 0.7
Li _xb La _yb Zr _zb M ^bb _{mb Onb}
5 ≦ xb ≦ 10, 1 ≦ yb ≦ 4, 1 ≦ zb ≦ 4, 0 ≦ mb ≦ 2, 5 ≦ nb ≦ 20
M ^bb is Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge,
At least one selected from the group consisting of In and Sn. Li _3.5 Zn _0.25 GeO ₄
・ LiTi ₂ P ₃ O ₁₂
Li _{1 + xh + yh} (Al, Ga) _xh (Ti, Ge) _2-xh Si _yh P _3-yh O ₁₂
0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1
・ Li ₃ PO ₄
・ LiPON
・ LiPOD ¹
D ¹ is Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
At least one selected from the group consisting of Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au. LiA ¹ ON
A ¹ is at least one selected from the group consisting of Si, B, Ge, Al, C, and Ga. <10> The solid electrolyte composition according to any one of <1> to <9>, including a dispersion medium object.
<11> The solid electrolyte composition according to any one of <1> to <10>, including an active material.
<12> An electrode sheet for an all-solid-state secondary battery formed by applying the solid electrolyte composition according to any one of <1> to <11> onto a metal foil.
<13> A method for producing an electrode sheet for an all-solid-state secondary battery, wherein the solid electrolyte composition according to any one of <1> to <11> is applied onto a metal foil to form a film.
The manufacturing method of the electrode sheet for all-solid-state secondary batteries as described in <13> including a <14> press process.
<15> Manufacture of an all-solid-state secondary battery that manufactures an all-solid-state secondary battery including a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer via the manufacturing method according to <13> or <14> Method.
<16> An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer is crystallized. A solid electrolyte composition comprising a crystalline oxide-based inorganic solid electrolyte and an amorphous oxide-based inorganic solid electrolyte, wherein the volume of the crystalline oxide-based inorganic solid electrolyte and the volume of the amorphous oxide-based inorganic solid electrolyte An all-solid secondary battery in which a solid electrolyte composition having a volume ratio of 70 to 99.8: 0.2 to 30 is applied to form a layer.

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, when it is simply described as “acryl”, it is used in the meaning including both methacryl and acrylic.

When the solid electrolyte composition of the present invention is used as a material for an inorganic solid electrolyte layer or an active material layer in an all-solid-state secondary battery, a layer can be formed without sintering. The solid secondary battery has an excellent effect of realizing good ionic conductivity.
Moreover, the electrode sheet for an all-solid-state secondary battery of the present invention can be suitably manufactured by using the solid electrolyte composition of the present invention, and the all-solid-state secondary battery of the present invention that exhibits the above-mentioned good performance. Can be used.
Furthermore, the electrode sheet for an all-solid secondary battery and the method for producing the all-solid-state secondary battery of the present invention can be suitably used for producing the electrode sheet for all-solid-state secondary battery and the all-solid-state secondary battery.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

FIG. 1 is a longitudinal sectional view schematically showing an all solid state secondary battery according to a preferred embodiment of the present invention. FIG. 2 is a longitudinal sectional view schematically showing the test apparatus used in the examples.

The all solid state secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer. In the present invention, at least one of the positive electrode active material layer, the negative electrode active material layer and the inorganic solid electrolyte layer is a solid electrolyte composition containing a crystalline oxide inorganic solid electrolyte and an amorphous oxide inorganic solid electrolyte. And applying a solid electrolyte composition in which the ratio of the volume of the crystalline oxide inorganic solid electrolyte to the volume of the amorphous oxide inorganic solid electrolyte is 70 to 99.8: 0.2 to 30 Form.
Hereinafter, the preferable embodiment will be described.

FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid-state secondary battery 10 of this embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order as viewed from the negative electrode side. . Each layer is in contact with each other and has a laminated structure. By adopting such a structure, at the time of charging, electrons (e ⁻ ) are supplied to the negative electrode side, and lithium ions (Li ⁺ ) are accumulated therein. On the other hand, at the time of discharge, lithium ions (Li ⁺ ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the working part 6. In the example shown in the figure, a light bulb is adopted as the operation part 6 and is turned on by discharge.

In this specification, the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an electrode layer. In addition, the electrode active material used in the present invention includes a positive electrode active material contained in the positive electrode active material layer and a negative electrode active material contained in the negative electrode active material layer. Sometimes referred to as an active material.

The thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. In consideration of general battery dimensions, the thickness is preferably 10 to 1,000 μm, more preferably 20 μm or more and less than 500 μm. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 is 50 μm or more and less than 500 μm.

<< Solid electrolyte composition >>
Hereinafter, the components contained in the solid electrolyte composition of the present invention will be described. The solid electrolyte composition of the present invention is preferably applied as a molding material for the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer constituting the all solid state secondary battery of the present invention.

(Inorganic solid electrolyte)
The inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of moving ions inside. Since it does not contain organic substances as the main ion conductive material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from the electrolyte salt). In addition, since the inorganic solid electrolyte is solid in a steady state, it is not usually dissociated or released into cations and anions. In this respect, it is also clearly distinguished from inorganic electrolyte salts (such as LiPF ₆ , LiBF ₄ , LiFSI, LiCl, etc.) in which cations and anions are dissociated or liberated in the electrolyte or polymer. The inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.

In the present invention, the inorganic solid electrolyte has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table. The solid electrolyte composition of the present invention contains (i) a crystalline oxide-based inorganic solid electrolyte and (ii) an amorphous oxide-based inorganic solid electrolyte, and (iii) the volume of the crystalline oxide-based inorganic solid electrolyte. And the volume of the amorphous oxide-based inorganic solid electrolyte are 70 to 99.8: 0.2 to 30. Hereinafter, the crystalline oxide inorganic solid electrolyte and the amorphous oxide inorganic solid electrolyte may be collectively referred to as an inorganic solid electrolyte.

(I) Crystalline oxide-based inorganic solid electrolyte “Crystalline oxide-based inorganic solid electrolyte” is an X-ray diffraction (XRD) measurement, which is separated into a crystal part (peak) and an amorphous part (halo), from the scattering intensity I _a of scattering intensity I _c and amorphous part of the crystal unit calculates the crystallinity X by the following formula (1), crystallinity X means 50 or more oxide based inorganic solid electrolytes.
_{X = I c / (I c} + I a) × 100 ··· Equation (1)
The crystalline oxide-based inorganic solid electrolyte used in the present invention contains an oxygen atom (O), has an ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is an electron. A compound having insulating properties is preferred.

As specific compound examples, for example, Li _xa La _ya TiO ₃ [xa and ya represent a composition ratio, and xa = 0.3 to 0.7, ya = 0.3 to 0.7. ] (LLT), Li _xb La _yb Zr _zb M ^bb _{mb Onb} (M ^bb is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn) , Xb satisfies 5 ≦ xb ≦ 10, yb satisfies 1 ≦ yb ≦ 4, zb satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, and nb satisfies 5 ≦ nb ≦ 20 . Incidentally, xb, the yb and zb represents the composition _{ratio.), Li xd (Al,} Ga) yd (Ti, Ge) zd Si ad P md O nd ( However, xd, yd, zd, ad , md and nd Represents a composition ratio, 1 ≦ xd ≦ 3, 0 ≦ yd ≦ 1, 0 ≦ zd ≦ 2, 0 ≦ ad ≦ 1, 1 ≦ md ≦ 7, 3 ≦ nd ≦ 13), Li _{(3- 2xe)} ^{M _ee} xe ^D _ee O synonymous with (formula below (II). ), Li ₂ O—SiO ₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₃ PO _{(4-3 / 2w)} N _w (w is w <1), LISICON (Lithium super ionic conductor) type crystal structure Li _3.5 Zn _0.25 GeO ₄ , La _0.55 Li _0.35 TiO ₃ having a perovskite type crystal structure, LiTi ₂ P ₃ O ₁₂ having a NASICON (Natium super ionic conductor) type crystal structure, Li _{1 + xh + yh} Al, Ga) _xh (Ti, Ge) _2-xh Si _yh P _3-yh O ₁₂ (where 0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1), Li ₇ La ₃ Zr ₂ O having a garnet-type crystal structure ₁₂ etc. are mentioned. Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li ₃ PO ₄ ), LiPON obtained by replacing a part of oxygen of lithium phosphate with nitrogen, LiPOD ¹ (D ¹ is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr) , Nb, Mo, Ru, Ag, Ta, W, Pt, Au, etc.). LiA ¹ ON (A ¹ is at least one selected from Si, B, Ge, Al, C, Ga, etc.) and the like can also be preferably used.
Among these, Li _xa La _ya TiO ₃ , Li _xb La _yb Zr _zb M ^bb _{mb Onb} , Li _3.5 Zn _0.25 GeO ₄ , LiTi ₂ P ₃ O ₁₂ , Li _{1 + xh + yh} (Al, Ga) _xh ( Ti, Ge) _2-xh Si _yh P _3-yh O ₁₂ , Li ₃ PO ₄ , LiPON, LiPOD ¹ and LiA ¹ ON are more preferred because of their high ionic conductivity.
These may be used alone or in combination of two or more. In addition, even if the composition is the same, depending on the preparation method, there is a crystallinity degree X of less than 50. Therefore, among the crystalline oxide inorganic solid electrolytes, the following amorphous oxide inorganic solid electrolytes should be used. Some can do it.

(Ii) Amorphous oxide-based inorganic solid electrolyte “Amorphous oxide-based inorganic solid electrolyte” is measured by X-ray diffraction (XRD) and separated into a crystal part (peak) and an amorphous part (halo). and calculates the crystallinity X from the scattering intensity I _a of scattering intensity I _c and amorphous part of the crystal unit in the above formula (1), crystallinity X means an oxide-based inorganic solid electrolyte of less than 50 .
The amorphous oxide-based inorganic solid electrolyte used in the present invention is not particularly limited, but may contain a compound represented by any one of the following formulas (I) to (IV), LiPON or Li ₃ PO _4. A compound represented by any one of the following formulas (I) to (IV) is more preferred, a compound represented by the following formula (I) or (II) is particularly preferred, and a compound represented by the following formula (I): The compounds represented are particularly preferred. When the amorphous oxide-based inorganic solid electrolyte is a compound represented by the following formula (I), the interface resistance can be more effectively reduced because it has a flexible structure and high ionic conductivity.
Hereinafter, the compound represented by the formula (I) will be described.

Li _{xc Byc} M ^cc _{zc Onc} formula (I)

In the formula (I), M ^cc is at least one selected from the group consisting of C, S, Al, Si, P, Ga, Ge, In and Sn, and xc, yc, zc and nc have a composition ratio. 0 <xc ≦ 5, 0 <yc ≦ 1, 0 ≦ zc ≦ 1, and 0 <nc ≦ 6.

As specific examples of the amorphous oxide based inorganic solid electrolyte comprising the compound represented by the above formula (I) and the compound represented by the above formula (I), Li ₃ BO ₃ , Li ₃ BO ₃ -Li ₂ SO ₄ , Li ₂ O—B ₂ O ₃ —P ₂ O ₅ , Li ₃ BO ₃ —Li ₂ CO _3, and Li ₃ BO ₃ —Li ₄ Si ₄ O ₄ may be mentioned and are preferably used in the present invention.

In addition, the compound represented by the said formula (I) can be prepared by a conventional method. For example, using Li ₃ BO ₃ , Li ₂ SO ₄ , Li ₂ CO ₃ , Li ₄ SiO ₄ , LiOH, H ₃ BO ₃ , SiO ₂ (the above raw materials may be hydrated) as a raw material, any It is possible to synthesize by combining the raw materials of the above into a zirconia (or alumina or stainless steel) vessel containing zirconia (or alumina or stainless steel) balls and stirring (mechanical milling) using a planetary ball mill. it can. The synthesis method is not limited to the above, and the synthesis may be performed by a flux method or a solid phase method.
Next, the compound represented by formula (II) will be described.

_{^{Li (3-2xe) M ee xe D}} ee O formula (II)

In formula (II), xe represents a number of 0 to ^{0.1, M ee} represents a divalent metal atom. D ^ee represents a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a combination of two or more halogen atoms.

Specific examples of the divalent metal atom represented by M ^ee include magnesium, calcium, strontium and barium, magnesium, calcium and barium are preferred, calcium and barium are more preferred, and barium is particularly preferred. D ^ee preferably contains a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom, a bromine atom, or a combination of a chlorine atom and a bromine atom, and even more preferably a chlorine atom.

Specific examples of the compound represented by the formula (II) include Li ₃ ClO, Li _2.99 Ba _0.005 ClO, Li _2.99 Ca _0.005 ClO, and Li _2.99 Mg _0.005 ClO. It is done.
The compound represented by the above formula (II) can be prepared by a conventional method. For example, LiF, LiCl, LiBr, LiI, LiOH, Ba (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ (the above raw materials may be hydrated) as raw materials. It can be synthesized by adding raw materials of any combination together with water into a Teflon (registered trademark) sealed container and heating. Moreover, you may synthesize | combine by the mechanical milling method or a solid-phase method.
Next, the compound represented by formula (III) will be described.

Li _xf Si _yf O _zf formula (III)

In the formula (III), xf, yf, and zf represent a composition ratio, and 1 ≦ xf ≦ 5, 0 <yf ≦ 3, and 1 ≦ zf ≦ 10.

Specific examples of the compound represented by the formula (III) include Li ₄ SiO ₄ and Li ₂ SiO ₃ .
The compound represented by the above formula (III) can be prepared by a conventional method. For example, it can be synthesized by mixing Li ₂ CO ₃ and SiO ₂ in a mortar, pelletizing and heat-treating, followed by mechanical milling. Alternatively, it may be synthesized by a solid phase method.
Next, the compound represented by formula (IV) will be described.

Li _xg S _yg O _zg formula (IV)

In the formula (IV), xg, yg and zg represent a composition ratio, and 1 ≦ xg ≦ 3, 0 <yg ≦ 2, and 1 ≦ zg ≦ 10.

Specific examples of the compound represented by the formula (IV) include Li ₂ SO ₄ and Li ₂ SO ₃ .
In addition, the compound represented by the said formula (IV) can be prepared by a conventional method. For example, a commercially available crystalline Li ₂ SO ₄ (manufactured by Wako Pure Chemical Industries, Ltd.) can be synthesized by making it amorphous by mechanical milling.

(Iii) Volume ratio In the solid electrolyte composition of the present invention, the ratio of the volume of the crystalline oxide inorganic solid electrolyte to the volume of the amorphous oxide inorganic solid electrolyte (volume of the crystalline oxide inorganic solid electrolyte) : Volume of amorphous oxide-based inorganic solid electrolyte) is 70 to 99.8: 0.2 to 30. When the volume ratio is within this range, in the solid electrolyte sheet, the electrode sheet for an all-solid secondary battery, and the all-solid secondary battery, which will be described later, good interface formation and high ion conductivity can be realized. When the volume of the amorphous oxide-based inorganic solid electrolyte is less than the lower limit of the above range, the interface formation is deteriorated and the resistance is increased. When the upper limit of the above range is exceeded, the ionic conductivity is lowered and the resistance is also increased.
In the solid electrolyte composition of the present invention, the ratio between the volume of the crystalline oxide-based inorganic solid electrolyte and the volume of the amorphous oxide-based inorganic solid electrolyte is from the viewpoint of achieving both interface formation and high ionic conductivity. 70 to 99: 1 to 30 is preferable, and 75 to 90:10 to 25 is more preferable.

In the solid electrolyte composition of the present invention, the ratio of the mass of the crystalline oxide-based inorganic solid electrolyte to the mass of the amorphous oxide-based inorganic solid electrolyte (the mass of the crystalline oxide-based inorganic solid electrolyte: amorphous The mass of the conductive oxide-based inorganic solid electrolyte is not particularly limited, but is preferably 70 to 99.5: 0.5 to 30, more preferably 80 to 98: 2 to 20, and particularly preferably 86 to 95: 5 to 14. preferable.

The volume average particle diameter of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.1 μm or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less. In addition, the measurement of the volume average particle diameter of an inorganic solid electrolyte is performed in the following procedures. An inorganic solid electrolyte is prepared by diluting a 1% by weight dispersion in a 20 ml sample bottle using water (heptane in the case of water labile substances). The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that. Using this dispersion liquid sample, using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA), data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Obtain the volume average particle size. For other detailed conditions, the description of JISZ8828: 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level, and the average value is adopted.

The content of the solid component in the solid electrolyte composition of the inorganic solid electrolyte is 100% by mass of the solid component when considering reduction of the interface resistance when used in an all-solid secondary battery and maintenance of the reduced interface resistance. Is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less.
In the present specification, the solid component refers to a component that does not disappear by volatilization or evaporation when dried at 170 ° C. for 6 hours. Typically, it refers to components other than the dispersion medium described below.
The said inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.

(binder)
The solid electrolyte composition of the present invention preferably contains at least one binder.
A solid oxide composition containing a crystalline oxide-based inorganic solid electrolyte, an amorphous oxide-based inorganic solid electrolyte, an active material, and a binder, The electrode layer of the solid secondary battery includes a binder as well as the active material and the inorganic solid electrolyte. Therefore, the contact area between the crystalline oxide inorganic solid electrolyte and the active material is increased via the amorphous oxide inorganic solid electrolyte and the binder, and the resistance at the interface can be suppressed. Furthermore, the binding between the solid particles, between the solid electrolyte layer and the electrode layer, and between the electrode layer and the current collector can be improved.

In the solid electrolyte composition of the present invention, the ratio of the volume of the crystalline oxide-based inorganic solid electrolyte to the volume of the amorphous oxide-based inorganic solid electrolyte and the volume of the binder (volume of the crystalline oxide-based inorganic solid electrolyte: non- The volume of the crystalline oxide inorganic solid electrolyte: the volume of the binder is preferably 70 to 99.8: 0.1 to 29.9: 0.1 to 29.9, and 70 to 95: 4.5 to 29. 5: 0.5 to 15 is more preferable, and 75 to 85:10 to 23: 2 to 5 is particularly preferable.
It is preferable to be within the above-mentioned range because ion conductivity, interface forming property, and binding property can be established in a solid electrolyte sheet and an all-solid secondary battery described later.

In the solid electrolyte composition of the present invention, the ratio of the mass of the crystalline oxide-based inorganic solid electrolyte to the mass of the amorphous oxide-based inorganic solid electrolyte and the mass of the binder (the mass of the crystalline oxide-based inorganic solid electrolyte) : Mass of amorphous oxide-based inorganic solid electrolyte: mass of binder) is preferably 70 to 99.5: 0.4 to 29.9: 0.1 to 29.6, and preferably 80 to 98: 1.5. To 19.5: 0.5 to 18.5 is more preferable, and 85 to 95: 4 to 14: 1 to 11 is particularly preferable.

The binder that can be used in the present invention preferably has at least one selected from the group consisting of the following functional group group [a].

Functional group [a]
Carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, hydroxy group, thiol (sulfanyl) group, isocyanato group, oxetanyl group, epoxy group, dicarboxylic acid anhydride group, silyl group

The binder that can be used in the present invention is not particularly limited as long as it is an organic polymer having at least one functional group selected from the functional group group [a].

When the binder has at least one functional group selected from the functional group group [a], it can form an interaction or bond with the inorganic solid electrolyte, and can realize high binding properties.

The functional group equivalent (the molecular weight of the binder having at least one functional group selected from the functional group [a] per functional group selected from the functional group [a]) is not particularly limited, but 50 Is preferably 50,000, more preferably 100 to 10,000, and particularly preferably 200 to 1,000.

In the present invention, the functional group group [a] is preferably the following functional group group [b] from the viewpoint of both the stability and the binding property of the binder.

Functional group [b]
Carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, hydroxy group, dicarboxylic anhydride group, silyl group

The resin constituting the binder that can be used in the present invention is preferably one that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited. In this specification, a polymer may be used as a term having the same meaning as a resin.
The binder that can be used in the present invention is preferably a resin having the functional group group [a], preferably the functional group group [b] described below. For example, fluorine-containing resin (for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP)), hydrocarbon resin (for example, polyethylene, polypropylene, Styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, polyisoprene), acrylic resin, vinyl resin, styrene resin, amide resin, imide resin, urethane resin, urea resin, polyester Examples thereof include resins, polyether resins, phenol resins, epoxy resins, polycarbonate resins, silicone resins, and combinations thereof. Among these, resins selected from the group consisting of hydrocarbon resins, fluororesins, acrylic resins, urethane resins (for example, polyurethane), polyamides, polyimides, polyethers, polyesters, and polycarbonates are preferable, and acrylic resins and polyurethanes are more preferable. .

Hereinafter, the resin constituting the binder that can be used in the present invention will be described in detail.

More preferably, the binder used in the present invention has a partial structure represented by the following formula (I).

In formula (I), R represents a hydrogen atom or a monovalent organic group.

Examples of the polymer having a partial structure represented by the formula (I) include a polymer having an amide bond, a polymer having a urea bond, a polymer having an imide bond, and a polymer having a urethane bond.

Examples of the organic group in R include an alkyl group, an alkenyl group, an aryl group, and a heteroaryl group. R is preferably a hydrogen atom.

-Polymer having amide bond Examples of the polymer having an amide bond include polyamide and polyacrylamide.
Polyamide can be obtained by condensation polymerization of a diamine compound and a dicarboxylic acid compound or ring-opening polymerization of a lactam.
Examples of the diamine compound include ethylenediamine, 1-methylethyldiamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine. And aliphatic diamine compounds such as dodecamethylenediamine, cyclohexanediamine, bis- (4,4′-aminohexyl) methane, and paraxylylenediamine. Moreover, as a diamine having a polypropyleneoxy chain, for example, a commercially available product “Jeffamine” series (trade name, manufactured by Huntsman, Mitsui Chemicals Fine) can be used. Examples of “Jeffamine” series include Jeffermin D-230, Jeffermin D-400, Jeffermin D-2000, Jeffermin XTJ-510, Jeffermin XTJ-500, Jeffermin XTJ-501, Jeffermin XTJ-502 , Jeffamine HK-511, Jeffamine EDR-148, Jeffamine XTJ-512, Jeffamine XTJ-542, Jeffamine XTJ-533, Jeffamine XTJ-536, and the like.
Examples of the dicarboxylic acid compound include, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, sebacic acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecadioic acid, and dimer acid, 1,4 -Cyclohexanedicarboxylic acid, paraxylylene dicarboxylic acid, metaxylylene dicarboxylic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid.

Specific examples of polyacrylamide include polyethylene glycol monomethyl ether acrylamide, polypropylene glycol monomethyl ether acrylamide, polyethylene glycol monomethyl ether methacrylamide, polypropylene glycol monomethyl ether methacrylamide, polyester methacrylamide, polycarbonate methacrylamide and the like.

-Polymer having a urea bond Polyurea may be mentioned as a polymer having a urea bond. Polyurea can be synthesized by condensation polymerization of a diisocyanate compound and a diamine compound in the presence of an amine catalyst.
Specific examples of the diisocyanate compound are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate Aromatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4′-methylenebis Cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) -diyl diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and the like; 1 mol of 1,3-butylene glycol and tolylene diisocyanate And a diisocyanate compound that is a reaction product of a diol such as an adduct with 2 mol and a diisocyanate. These may be used individually by 1 type and may use 2 or more types together. Among these, 4,4′-diphenylmethane diisocyanate (MDI) and 4,4′-methylenebis (cyclohexyl isocyanate) are preferable.
Specific examples of the diamine compound include the compound examples described above.

-Polymer which has an imide bond As a polymer which has an imide bond, a polyimide is mentioned. A polyimide is obtained by ring-closing after forming a polyamic acid by addition-reacting a tetracarboxylic dianhydride and a diamine compound.
Specific examples of tetracarboxylic dianhydrides include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and pyromellitic dianhydride (PMDA), 2,3,3. ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), oxydiphthalic dianhydride, diphenylsulfone-3,4,3', 4'-tetracarboxylic dianhydride, bis (3,4- Dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis ( 3,4-dicarboki Siphenyl) propane dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), p-biphenylenebis (trimellitic acid monoester acid anhydride), m-terphenyl-3,4,3 ′, 4 '-Tetracarboxylic dianhydride, p-terphenyl-3,4,3', 4'-tetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-di Carboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 ′-(2, 2-F Sa fluoro isopropylidene) diphthalic acid dianhydride, and the like. These may be used alone or in combination of two or more.
The tetracarboxylic acid component preferably contains at least one of s-BPDA and PMDA. For example, s-BPDA is preferably 50 mol% or more, more preferably 70 mol% or more in 100 mol% of the tetracarboxylic acid component. Especially preferably, it contains 75 mol% or more. The tetracarboxylic dianhydride preferably has a rigid benzene ring.

Specific examples of the diamine compound include the compound examples described above.
The diamine compound preferably has a structure having amino groups at both ends of a polyethylene oxide chain, a polypropylene oxide chain, a polycarbonate chain, or a polyester chain.

-Polymer which has a urethane bond As a polymer which has a urethane bond, a polyurethane is mentioned. Polyurethane is obtained by condensation polymerization of a diisocyanate compound and a diol compound in the presence of a titanium, tin, or bismuth catalyst.
Examples of the diisocyanate compound include the compound examples described above.
Specific examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and polyethylene glycol (for example, average molecular weight 200, 400, 600, 1000, 1500, 2000, 3000, 7500 Polyethylene glycol), polypropylene glycol (for example, polypropylene glycol with an average molecular weight of 400, 700, 1000, 2000, 3000, or 4000), neopentyl glycol, 1,3-butylene glycol, 1,4-butanediol, 1,3 -Butanediol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis- -Hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, bisphenol And propylene oxide adduct of F.

The diol compound is also available as a commercial product, and examples thereof include polyether diol compounds, polyester diol compounds, polycarbonate diol compounds, polyalkylene diol compounds, and silicone diol compounds.

The diol compound preferably has at least one of a polyethylene oxide chain, a polypropylene oxide chain, a polycarbonate chain, a polyester chain, a polybutadiene chain, a polyisoprene chain, a polyalkylene chain, and a silicone chain. In addition, the diol compound has a carbon-carbon unsaturated bond and a polar group (alcoholic hydroxyl group, phenolic hydroxyl group, sulfanyl group, carboxy group, sulfo group, A sulfonamide group, a phosphoric acid group, a nitrile group, an amino group, a zwitterion-containing group, a metal hydroxide, and a metal alkoxide). As the diol compound, for example, 2,2-bis (hydroxymethyl) propionic acid can be used. As the diol compound containing a carbon-carbon unsaturated bond, commercially available products such as Blemmer GLM (manufactured by NOF Corporation) and JP-A No. 2007-187836 can be preferably used.

In the case of polyurethane, monoalcohol or monoamine can be used as a polymerization terminator. The polymerization terminator is introduced into the terminal site of the polyurethane main chain. Polyalkylene glycol monoalkyl ether (polyethylene glycol monoalkyl ether and polypropylene monoalkyl ether are preferred), polycarbonate diol monoalkyl ether, polyester diol monoalkyl ether, polyester monoalcohol, etc. Can be used.

Also, by using a monoalcohol or monoamine having a polar group or carbon-carbon unsaturated bond, it is possible to introduce a polar group or carbon-carbon unsaturated bond at the end of the polyurethane main chain. For example, hydroxyacetic acid, hydroxypropionic acid, 4-hydroxybenzyl alcohol, 3-mercapto-1-propanol, 2,3-dimercapto-1-propanol, 3-mercapto-1-hexanol, 3-hydroxypropanesulfonic acid, 2-cyano Examples include ethanol, 3-hydroxyglutaronitrile, 2-aminoethanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N-methacrylenediamine, and the like.

Acrylic resin and vinyl resin As acrylic resin and vinyl resin, from the viewpoint of low battery resistance and improved ionic conductivity, repeating units derived from macromonomer (X) having a mass average molecular weight of 1,000 or more as a side chain component Binder particles in which is incorporated are preferred. Hereinafter, the main chain component and the side chain component constituting the acrylic resin and the vinyl resin will be described.
-Main chain component The main chain of the polymer forming the acrylic resin and the vinyl resin is not particularly limited, and a normal polymer component can be applied. The monomer constituting the main chain component is preferably a monomer having a polymerizable unsaturated bond, and for example, various vinyl monomers and acrylic monomers can be applied. As the acrylic monomer, it is preferable to use a monomer selected from (meth) acrylic acid monomers, (meth) acrylic acid ester monomers, and (meth) acrylonitrile. The number of polymerizable groups is not particularly limited, but is preferably 1 to 4.
Examples of the monomer constituting the main chain include monomers described in paragraphs 0041 and 0042 of International Publication No. 2015/046314. Among these, it is preferable to contain the following monomers. In the following exemplary compounds, n represents the number of repeating units.

-Side chain component The macromonomer (X) has a mass average molecular weight of 1,000 or more, more preferably 2,000 or more, and particularly preferably 3,000 or more. The upper limit is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less. When the binder has a side chain having a molecular weight in the above range, it can be more uniformly dispersed in the organic solvent and can be mixed and applied with the solid electrolyte particles.
The mass average molecular weight of the macromonomer can be measured by the same method as the method for measuring the molecular weight of the binder in the section of Examples described later.

The SP value of the macromonomer (X) is preferably 10 or less, and more preferably 9.5 or less. Although there is no particular lower limit, it is practical that it is 5 or more.

-SP value definition-
In this specification, unless otherwise specified, the SP value is obtained by the Hoy method (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^−3/2 . Note that the SP value of the side chain component (X) is not substantially different from the SP value of the raw material monomer forming the side chain, and may be evaluated accordingly.

The SP value is an index indicating the characteristic of being dispersed in an organic solvent. Here, by setting the side chain component to a specific molecular weight or more, preferably to the SP value or more, the binding property with the solid electrolyte is improved, thereby improving the affinity with the solvent and stably dispersing. This is preferable.

The above macromonomer (X) is not particularly limited, and ordinary polymer components can be applied. Macromonomers described in paragraphs 0046 to 0067 of JP-A-2015-088486 are preferred. The macromonomer (X) preferably has a polymerizable unsaturated bond, and can have, for example, various vinyl groups or (meth) acryloyl groups. In the present invention, it is preferable to have a (meth) acryloyl group.

The binder used in the present invention is preferably polymer particles, and the lower limit of the average particle diameter of the polymer particles is preferably 0.01 μm or more, and more preferably 0.05 μm or more. On the other hand, the upper limit of the average particle diameter of the polymer particles is preferably 50 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. It is preferable from a viewpoint of an output density improvement that an average particle diameter exists in the said preferable range.
Here, the “polymer particles” refer to particles that do not dissolve even when added to the dispersion medium described later and are dispersed in the dispersion medium in the form of particles and exhibit an average particle diameter of more than 0.01 μm.

Unless otherwise specified, the average particle size of the polymer particles used in the present invention shall be based on the measurement conditions and definitions described below.
The polymer particles are diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used for preparing the solid electrolyte composition, for example, heptane). The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that. Using this dispersion liquid sample, using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA), data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Let the obtained volume average particle diameter be an average particle diameter. For other detailed conditions, the description of JISZ8828: 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level and measured, and the average value is adopted.
In addition, the measurement from the produced all-solid-state secondary battery is performed, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method for measuring the average particle diameter of the polymer particles, This can be done by eliminating the measured value of the average particle diameter of the particles other than the polymer particles that have been measured.

The structure of the polymer particle is not particularly limited as long as it is an organic polymer particle. Examples of the resin constituting the organic polymer particles include the resins described as the resin constituting the binder, and preferred resins are also applied.

The shape of the polymer particles is not limited as long as they are solid. The polymer particles may be monodispersed or polydispersed. The polymer particles may be spherical or flat and may be amorphous. The surface of the polymer particles may be smooth or may have an uneven shape. The polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.

The polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form as the molecular weight increases.
Moreover, you may use the method of crushing the existing polymer mechanically, and the method of making a polymer liquid fine particle by reprecipitation.

As the polymer particles, for example, commercially available products can be used, and specific examples include the following commercially available products (all are trade names, and the numerical values in parentheses indicate the average particle diameter). The polymer particles that can be used in the present invention are not limited to these.

Fluorine resin particle microdispers series (manufactured by Techno Chemical Co., Ltd., for example, microdispers-200 (PTFE particles, 200 nm), microdispers-3000 (PTFE particles 3 μm), microdispers-8000 (PTFE particles) , 8 μm)), Disperse Easy-300 (PTFE particles, 200 nm, manufactured by Techno Chemical Co., Ltd.),
FluonAD series (Asahi Glass Co., Ltd., for example, FluonAD911E, FluonAD915E, FluonAD916E, FluonAD939E),
Algoflon series (manufactured by Solvay Co., Ltd., for example, Algoflon F (PTFE particles, 15 to 35 μm), Algoflon S (PTFE particles, 15 to 35 μm)),
Lubron series (Daikin Co., Ltd., for example, Lubron L-2 (PTFE particles, 3.5 μm), Lubron L-5 (PTFE particles, 5 μm), Lubron L-5F (PTFE particles, 4.5 μm))

・ Hydrocarbon resin particle soft beads, Saixen (polyolefin emulsion), Sepoljon G (polyolefin emulsion), Sepolex IR100 (polyisoprene latex), Sepolex CSM (chlorosulfonated polyethylene latex), Frocene (polyethylene powder), Frocene UF (polyethylene powder) ), Flowbrene (polypropylene powder), flow beads (polyethylene-acrylic copolymer powder) (all manufactured by Sumitomo Seika Co., Ltd.)

・ Styrene resin particle Chemisnow KSR-3A (manufactured by Soken Chemical Co., Ltd.), Eposter ST (manufactured by Nippon Shokubai Co., Ltd.)

・ Amide resin particle separsion PA (copolymerized nylon emulsion, manufactured by Sumitomo Seika Co., Ltd.), Trepearl PAI (polyamideimide particles, manufactured by Toray Industries, Inc.)

-Imide resin particle polyimide powder P84 (R) NT (manufactured by Daicel Evonik Co., Ltd.),
Polyimide powder PIP-3, polyimide powder PIP-25, polyimide powder PIP-60 (all manufactured by Seishin Enterprise Co., Ltd.)
Polyimide powder UIP-R, polyimide powder UIP-S (both manufactured by Ube Industries, Ltd.)

Urethane resin particle dimic beads UCN-8070CM (7 μm), dimic beads UCN-8150CM (15 μm) (both manufactured by Dainichi Seika Co., Ltd.),
Art Pearl Series (Negami Kogyo Co., Ltd., for example, Art Pearl C, Art Pearl P, Art Pearl JB, Art Pearl U, Art Pearl CE, Art Pearl AK, Art Pearl HI, Art Pearl MM, Art Pearl FF, Art Pearl TK, Art Pearl C-TH, Art Pearl RW, Art Pearl RX, Art Pearl RY, Art Pearl RZ, Art Pearl RU, Art Pearl RV, Art Pearl BP),
Grosdale S Series, Grosdale M Series, Grosdale V Series, Grosdale T Series (all manufactured by Mitsui Chemicals)
Infinergy (BASF)

-Urea resin particles As the urea resin particles, particles of a polymer having a urea bond described in International Publication No. 2015/046313 are preferably used.

・ Polyester resin particle Sepulsion ES (copolymerized polyester emulsion, manufactured by Sumitomo Seika Co., Ltd.)

・ Polyether resin particles Trepearl PPS (polyphenylene sulfide particles, manufactured by Toray Industries, Inc.), Trepal PES (Polyethersulfone particles, manufactured by Toray Industries, Inc.)

・ Phenol resin particle LPS series (manufactured by Lignite Co., Ltd.), Marilyn FM series (manufactured by Gunei Chemical Industry Co., Ltd.), Marilyn HF series (manufactured by Gunei Chemical Industry Co., Ltd.)

・ Epoxy resin particles Trepal EP (epoxy resin particles, manufactured by Toray Industries, Inc.)

-Polycarbonate resin particle The polycarbonate resin particle can use the particle | grains of the polycarbonate resin synthesize | combined by the method as described in international publication 2011/004730 pamphlet, for example. Specifically, the polycarbonate resin can be polymerized by reacting an epoxy compound with carbon dioxide.

Silicone resin particle Seahoster KE series (manufactured by Nippon Shokubai Co., Ltd., for example, Seahoster KE-E series, Seahoster KE-W series, Seahoster KE-P series, Seahoster KE-S series),
Silicone composite powder series (for example, silicone composite powder KMP-600, silicone composite powder KMP-601, silicone composite powder KMP-602, silicone composite powder KMP-605, silicone composite powder X-52-7030), silicone resin powder series ( For example, silicone resin powder KMP-590, silicone resin powder KMP-701, silicone resin powder X-52-854, silicone resin powder X-52-1621), silicone rubber powder series (for example, silicone rubber powder KMP-597, silicone Rubber powder KMP-598, silicone rubber powder KMP-594, silicone rubber powder X-52-875 ) Made by the company),
Charine R-170S (silicone acrylic copolymer, manufactured by Nissin Chemical Industry Co., Ltd.)

The upper limit of the glass transition temperature of the binder is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, and most preferably −20 ° C. or lower. The lower limit is preferably −100 ° C. or higher, more preferably −70 ° C. or higher, and most preferably −50 ° C. or higher.

The glass transition temperature (Tg) is measured by using a differential scanning calorimeter “X-DSC7000” (manufactured by SII Nanotechnology Co., Ltd.) under the following conditions using a dry sample. The measurement is performed twice on the same sample, and the second measurement result is adopted.
Measurement chamber atmosphere: Nitrogen (50 mL / min)
Temperature increase rate: 5 ° C / min
Measurement start temperature: -100 ° C
Measurement end temperature: 200 ° C
Sample pan: Aluminum pan Mass of measurement sample: 5 mg
Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.

The water concentration of the polymer (preferably polymer particles) constituting the binder used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
Moreover, the polymer which comprises the binder used for this invention may be crystallized and dried, and the polymer solution may be used as it is. It is preferable that the amount of metal catalyst (urethane-forming, polyester-forming catalyst, tin, titanium, bismuth catalyst) is small. It is preferable that the metal concentration in the copolymer be 100 ppm (mass basis) or less by reducing the amount during polymerization or removing the catalyst by crystallization.

The solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte or the active material and that does not decompose them. For example, hydrocarbon solvents (toluene, heptane, xylene), ester solvents (ethyl acetate, propylene glycol monomethyl ether acetate), ether solvents (tetrahydrofuran, dioxane, 1,2-diethoxyethane), ketone solvents (acetone) , Methyl ethyl ketone, cyclohexanone), nitrile solvents (acetonitrile, propionitrile, butyronitrile, isobutyronitrile), halogen solvents (dichloromethane, chloroform) and the like.

The polymer constituting the binder used in the present invention preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable.
In the present invention, the molecular weight of the polymer means a mass average molecular weight unless otherwise specified.
The mass average molecular weight of the polymer can be measured by the same method as the method for measuring the molecular weight of the binder in the section of Examples described later.

(Dispersant)
The solid electrolyte composition of the present invention preferably contains a dispersant. By adding a dispersant, even when the content of either the electrode active material or the inorganic solid electrolyte is large, the aggregation can be suppressed, and a uniform electrode layer and solid electrolyte layer can be formed. There is an effect.

The dispersant is a compound having a molecular weight of 200 or more and less than 3000, and at least one selected from the functional group represented by the functional group (A) is the same as an alkyl group having 8 or more carbon atoms or an aryl group having 10 or more carbon atoms. It is preferably contained in the molecule.
Functional group (A): acidic group, group having basic nitrogen atom, (meth) acryl group, (meth) acrylamide group, alkoxysilyl group, epoxy group, oxetanyl group, isocyanato group, cyano group, sulfanyl group and hydroxy Base

The molecular weight of the dispersant is preferably 300 or more and less than 2,000, more preferably 500 or more and less than 1,000. When it is less than the above upper limit value, the aggregation of particles is less likely to occur, and the reduction in output can be effectively suppressed. Moreover, it becomes difficult to volatilize in the step which apply | coats and dries a solid electrolyte composition slurry as it is more than the said lower limit.

The content of the dispersing agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and more preferably 1 to 3% by mass with respect to the total solid components of the solid electrolyte composition of the present invention.

(Lithium salt)
The solid electrolyte composition of the present invention preferably contains a lithium salt.
The lithium salt is preferably a lithium salt usually used in this type of product, and is not particularly limited. For example, the lithium salts described in paragraphs 0082 to 0085 of JP-A-2015-088486 are preferable.

The content of the lithium salt is preferably 0 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte. As an upper limit, 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.

(Conductive aid)
Next, the conductive additive that can be used in the solid electrolyte composition of the present invention will be described. What is known as a general conductive support agent can be used. For example, graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fiber and carbon nanotubes, which are electron conductive materials Carbon fibers such as graphene, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, and metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives may be used. It may be used. Moreover, 1 type may be used among these and 2 or more types may be used.

(Positive electrode active material)
Next, the positive electrode active material that can be used in the solid electrolyte composition of the present invention will be described. When the solid electrolyte composition of the present invention is used as a material for forming a positive electrode active material layer, the solid electrolyte composition of the present invention contains a positive electrode active material.
The positive electrode active material is preferably one that can reversibly insert and release lithium ions. The material is not particularly limited, and may be a transition metal oxide or an element that can be combined with Li such as sulfur. Among them, it is preferable to use a transition metal oxide, and it is more preferable to have one or more elements selected from Co, Ni, Fe, Mn, Cu, and V as a transition metal element. Specific examples of transition metal oxides include (MA) transition metal compounds having a layered rock salt structure, (MB) transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD) Examples include lithium-containing transition metal halide phosphate compounds, (ME) lithium-containing transition metal silicates, and the like.
(MA) As specific examples of transition metal compounds having a layered rock salt structure, LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate) LiNi _0.85 Co _0.1 Al _0.05 O ₂ (nickel cobalt lithium aluminum oxide [NCA]), LiNi _0.33 Co _0.33 Mn _0.33 O ₂ (nickel manganese lithium cobalt oxide [NMC]), LiNi _0.5 Mn _0.5 O ₂ (manganese nickel) Acid lithium).
Specific examples of the transition metal oxide having an (MB) spinel structure include LiCoMnO _4, Li ₂ FeMn ₃ O ₈ , Li ₂ CuMn ₃ O ₈ , Li ₂ CrMn ₃ O _{8, and} Li ₂ NiMn ₃ O _8. .
Examples of (MC) lithium-containing transition metal phosphates include olivine-type iron phosphate salts such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , LiCoPO _{4 and the} like. And monoclinic Nasicon type vanadium phosphate salts such as Li ₃ V ₂ (PO ₄ ) ₃ (vanadium lithium phosphate).
The (MD) lithium-containing transition metal halide phosphorus oxide, for _example, Li 2 FePO ₄ F such fluorinated phosphorus iron _salt, Li 2 MnPO ₄ hexafluorophosphate manganese salts such as _F, Li 2 CoPO ₄ F Cobalt fluorophosphates such as
Examples of the (ME) lithium-containing transition metal silicate include Li ₂ FeSiO ₄ , Li ₂ MnSiO ₄ , Li ₂ CoSiO _{4, and the} like.

The volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material that can be used in the solid electrolyte composition of the present invention is not particularly limited. In addition, 0.1 μm to 50 μm is preferable. In order to make the positive electrode active substance have a predetermined particle size, a normal pulverizer or classifier may be used. The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent. The volume average particle diameter of the positive electrode active material can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).

The concentration of the positive electrode active material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass in 100% by mass of the solid component in the solid electrolyte composition for forming the positive electrode active material layer.

The positive electrode active materials may be used singly or in combination of two or more.

(Negative electrode active material)
Next, the negative electrode active material that can be used in the solid electrolyte composition of the present invention will be described. When the solid electrolyte composition of the present invention is used as a material for forming a negative electrode active material layer, the solid electrolyte composition of the present invention contains a negative electrode active material.
As the negative electrode active material, those capable of reversibly inserting and releasing lithium ions are preferable. The material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as a simple substance of lithium or a lithium aluminum alloy, Sn, Si, Al, In, etc. And metals that can form an alloy with lithium. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. In addition, the metal composite oxide is preferably capable of inserting and extracting lithium. The material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.

The carbonaceous material used as the negative electrode active material is a material substantially made of carbon. Examples thereof include carbonaceous materials obtained by firing various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN (polyacrylonitrile) -based resins and furfuryl alcohol resins. Further, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, etc. And mesophase microspheres, graphite whiskers, flat graphite and the like.

As the metal oxide and metal composite oxide applied as the negative electrode active material, an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done. The term “amorphous” as used herein means an X-ray diffraction method using CuKα rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2θ, and is a crystalline diffraction line. You may have. The strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.

Among the group of compounds consisting of the above amorphous oxide and chalcogenide, amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable. Particularly preferred are oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga ₂ O ₃ , SiO, GeO, SnO, SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , SnSiO ₃ , GeS, SnS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S ₃ , Sb ₂ S ₅ , such as SnSiS ₃ may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li ₂ SnO ₂ .

The volume average particle diameter of the negative electrode active material is preferably 0.1 μm to 60 μm. In order to obtain a predetermined particle size, an arbitrary pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used. When pulverizing, wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary. In order to obtain a desired particle diameter, classification is preferably performed. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet. The volume average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.

It is also preferable that the negative electrode active material contains a titanium atom. More specifically, since Li ₄ Ti ₅ O ₁₂ has a small volume fluctuation at the time of occlusion and release of lithium ions, it has excellent rapid charge / discharge characteristics, suppresses electrode deterioration, and improves the life of lithium ion secondary batteries. This is preferable.

The concentration of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in 100% by mass of the solid component in the solid electrolyte composition.

The negative electrode active materials may be used alone or in combination of two or more.

(Dispersion medium)
The solid electrolyte composition of the present invention preferably contains a dispersion medium in order to disperse each of the above components. Specific examples of the dispersion medium include the following.

Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.

Examples of ether compound solvents include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene. Glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and dioxane.

Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone (NMP), 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, Examples include formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, and the like.

Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.

Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the aromatic compound solvent include benzene, toluene, xylene and the like.

Examples of the aliphatic compound solvent include hexane, heptane, octane, decane and the like.

Examples of the nitrile compound solvent include acetonitrile, propyronitrile, butyronitrile, and the like.

Examples of the non-aqueous dispersion medium include the above aromatic compound solvents and aliphatic compound solvents.

In the present invention, among these, aliphatic compound solvents, aromatic compound solvents and amide compound solvents are preferred, heptane, toluene and NMP are more preferred, and heptane is particularly preferred.

The dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 70 ° C. or higher at normal pressure (1 atm). The upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower. The said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.

The content of the dispersion medium with respect to the total mass of 100 parts by mass of the solid electrolyte composition is preferably 5 to 95 parts by mass, preferably 10 to 90 parts by mass, and more preferably 30 to 70 parts by mass.

<Preparation of all-solid secondary battery>
The all-solid-state secondary battery may be manufactured by a conventional method. Specifically, the solid electrolyte composition of this invention is apply | coated on the metal foil used as a collector, and the method of setting it as the electrode sheet for all-solid-state secondary batteries which formed the coating film is mentioned.
For example, the solid electrolyte composition of the present invention as a positive electrode material is applied onto a metal foil that is a positive electrode current collector to form a positive electrode active material layer, and a positive electrode sheet for an all-solid secondary battery is produced. On the positive electrode active material layer, the solid electrolyte composition of the present invention as a solid electrolyte layer material is applied to form a solid electrolyte layer. Furthermore, on the solid electrolyte layer, the solid electrolyte composition of the present invention as a negative electrode material is applied to form a negative electrode active material layer. The structure of an all-solid-state secondary battery in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer by overlapping a negative electrode current collector (metal foil) on the negative electrode active material layer Can be obtained.

In the all solid state secondary battery of the present invention, the electrode layer contains an active material. From the viewpoint of improving ion conductivity, the electrode layer preferably contains the inorganic solid electrolyte. The electrode layer preferably contains a binder from the viewpoint of improving the binding between the solid particles, between the electrode layer and the solid electrolyte layer, and between the electrode layer and the current collector.
The solid electrolyte layer contains an inorganic solid electrolyte. From the viewpoint of improving the binding between the solid particles and between the layers, the solid electrolyte layer preferably contains a binder.

In addition, the application | coating method of said each composition should just be based on a conventional method. At this time, the composition for forming the positive electrode active material layer, the composition for forming the inorganic solid electrolyte layer, and the composition for forming the negative electrode active material layer may be subjected to a drying treatment after being applied. Alternatively, after the multilayer coating, a drying process may be performed. The drying temperature is not particularly limited. The lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and the upper limit is preferably 300 ° C or lower, more preferably 250 ° C or lower. By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state.

The all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, portable tape recorder, radio, backup power supply, memory card, etc. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.

Especially, it is preferable to apply to applications that require high capacity and high rate discharge characteristics. For example, in power storage facilities and the like that are expected to increase in capacity in the future, high safety is essential, and further compatibility with battery performance is required. In addition, electric vehicles and the like are equipped with a high-capacity secondary battery and are expected to be charged every day at home, and further safety is required against overcharging. According to the present invention, it is possible to exhibit the excellent effect correspondingly to such a usage pattern.

According to a preferred embodiment of the present invention, the following applications are derived.
[1] An all-solid secondary battery in which at least one of a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer contains a lithium salt.
[2] All-solid-state secondary battery in which the solid electrolyte layer is formed by wet-coating a slurry in which a crystalline oxide inorganic solid electrolyte and an amorphous oxide inorganic solid electrolyte are dispersed by a non-aqueous dispersion medium Manufacturing method.
[3] A solid electrolyte composition for producing the all-solid secondary battery.
[4] An electrode sheet for an all-solid-state secondary battery, wherein the solid electrolyte composition is applied onto a metal foil and formed into a film.
[5] A method for producing an electrode sheet for an all-solid-state secondary battery, in which the solid electrolyte composition is applied onto a metal foil to form a film.
Examples of the method of applying the solid electrolyte composition on the metal foil include coating (wet coating, spray coating, spin coating coating, slit coating, stripe coating, bar coating coating dip coating), and wet coating. preferable.

As described in [2] and [5] of the preferred embodiments, both the all-solid secondary battery and the method for producing an electrode sheet for an all-solid secondary battery of the present invention are wet processes. According to the wet process, an all-solid-state secondary battery and an electrode sheet for an all-solid-state secondary battery can be produced without causing impurities as in the case of sintering.

An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte. In this, this invention presupposes an inorganic all-solid-state secondary battery. The all-solid-state secondary battery is classified into an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above LLT, LLZ, or the like. Note that the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte.
The inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the LLT and LLZ. The inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function. On the other hand, a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations (Li ions) is sometimes called an electrolyte. When distinguishing from the electrolyte as the above ion transport material, this is called “electrolyte salt” or “supporting electrolyte”. An example of the electrolyte salt is LiTFSI.
In the present invention, the term “composition” means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.

Hereinafter, the present invention will be described in more detail based on examples. The present invention is not construed as being limited thereby. In the following examples, “parts” and “%” are based on mass unless otherwise specified. “Room temperature” means 25 ° C.

<Preparation of amorphous oxide-based inorganic solid electrolyte>
-Preparation of amorphous oxide-based inorganic solid electrolyte LBO-
Li ₂ O (Aldrich Corp. _{purity> 97%) 3.000g, B 2} O 3 (Aldrich Corp. purity> 99.98%) 2.330g argon atmosphere (dew point -60 ° C. or less) in an agate mortar under The mixture was added and mixed for 5 minutes using an agate pestle. The obtained mixture was placed in an alumina crucible and heated at 500 ° C. for 1 hour in the atmosphere. 180 zirconia beads having a diameter of 5 mm were placed in a 45 mL container (manufactured by Fritsch) made of zirconia, the above mixture was added, and the container was completely sealed under an argon atmosphere. An amorphous oxide-based inorganic solid electrolyte LBO (Li ₃ BO ₃ ) is set by setting a container on a planetary ball mill P-7 (trade name) manufactured by Fricht and performing mechanical milling at a temperature of 25 ° C. and a rotational speed of 400 rpm for 40 hours. Got.

-Preparation of amorphous oxide-based inorganic solid electrolyte LBO-LSO-
Li ₂ SO ₄ .H ₂ O (purity> 99.9%, manufactured by Aldrich) was dehydrated by heating at 300 ° C. for 2 hours under a nitrogen atmosphere to obtain Li ₂ SO ₄ . Under an argon atmosphere (dew point: −60 ° C. or lower), the above-mentioned dry Li ₂ SO ₄ : 0.611 g, Li ₃ BO ₃ (manufactured by Wako Pure Chemical Industries, Ltd.): 3.982 g are weighed and put into an agate mortar. Mix for 5 minutes using a pestle. 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, a mixture of Li ₂ SO ₄ and Li ₃ BO ₃ was added, and the container was completely sealed under an argon atmosphere. A container is set in a planetary ball mill P-7 manufactured by Fricht Co. and subjected to mechanical milling for 40 hours at a temperature of 25 ° C. and a rotational speed of 400 rpm, thereby producing an amorphous oxide-based inorganic solid electrolyte LBO-LSO (Li ₃ BO ₃ -Li ₂ SO ₄₎ was obtained.

<Synthesis of binder>
-Synthesis of Binder B-1-
In order to synthesize Binder B-1, first, macromonomer M-1 was synthesized.
Specifically, 190 parts by mass of toluene was added to a 1 L three-necked flask equipped with a reflux condenser and a gas introduction cock, nitrogen gas was introduced at a flow rate of 200 mL / min for 10 minutes, and the temperature was raised to 80 ° C. Components shown in the following composition 1 were mixed in a separate container, and the mixed liquid was added dropwise to toluene over 2 hours, and then stirred at 80 ° C. for 2 hours. Thereafter, 0.2 g of V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at 95 ° C. for 2 hours. 0.025 parts by mass of 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 13 parts by mass and 2.5 parts by mass of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 120 ° C. for 3 hours in the atmosphere. After cooling the reaction solution to room temperature, it was added to methanol for precipitation, decanted, and the supernatant was removed. The precipitate was washed twice with methanol and then blown and dried at 50 ° C. The obtained solid was dissolved in 300 parts by mass of heptane to obtain a solution of macromonomer M-1. The solid content concentration was 43.4%, the SP value was 9.1, and the mass average molecular weight was 16,000.

(Composition 1)
Dodecyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 150 parts by mass Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 59 parts by mass 3-mercaptoisobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts by mass V-601 (trade name, Wako Pure Chemical Industries, Ltd.) 1.9 parts by mass

Next, binder B-1 was synthesized using the macromonomer M-1.
Specifically, in a 1 L three-necked flask equipped with a reflux condenser and a gas introduction cock, 47 parts by mass of the synthesized macromonomer M-1 heptane solution (solid content concentration: 43.4%) and 60 parts by mass of heptane. After adding nitrogen gas at a flow rate of 200 mL / min for 10 minutes, the temperature was raised to 80 ° C. Components shown in the following composition 2 were mixed in a separate container, and the mixed liquid was added dropwise over 2 hours, followed by stirring at 80 ° C. for 2 hours. Thereafter, 0.2 g of V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at 95 ° C. for 2 hours. After cooling to room temperature, 300 mL of heptane was added to obtain a dispersion of polymer B-1.

(Composition 2)
Heptane solution of the above synthesized macromonomer M-1 (solid content concentration: 43.4%)
93 parts by mass Butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 100 parts by mass Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 20 parts by mass Acrylic acid (trade name: a-101, manufactured by Wako Pure Chemical Industries, Ltd.) 20 parts by mass Part V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts by mass

-Synthesis of Binder B-2-
A binder B-2 was synthesized in the same manner as the binder B-1, except that the acrylic acid having the composition 2 was changed to glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.).

-Synthesis of Binder B-3-
In order to synthesize Binder B-3, first, polyurea colloidal particles Aa-1 were synthesized.
Specifically, 260 g of a heptane solution containing 25% by mass of terminal diol-modified polydodecyl methacrylate (Ab-1: a diol compound having a long-chain alkyl group having 6 or more carbon atoms) was added to a 1 L three-necked flask, and heptane was added. Diluted with 110 g. To this were added 11.1 g of isophorone diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.1 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.), and the mixture was heated and stirred at 75 ° C. for 5 hours. Thereafter, a diluted solution of 125 g of heptane of 0.4 g of isophoronediamine (amine compound) was dropped over 1 hour. The polymer solution changed from a transparent solution to a pale yellow fluorescent color 10 minutes after the start of dropping. It was confirmed that a urea colloid was formed by this change. The reaction solution was cooled to room temperature to obtain 506 g of a 15 mass% heptane solution of polyurea colloidal particles Aa-1.
In the polyurea colloidal particle Aa-1, the dodecyl group of the terminal diol-modified polydodecyl methacrylate is a structural part solvated with heptane (hydrocarbon solvent), and the polyurea structure is a structural part that is not solvated with heptane.
The mass average molecular weight of the polyurea of the polyurea colloidal particles Aa-1 was 9,600.

Next, binder B-3 was synthesized using polyurea colloidal particles Aa-1.
Specifically, 2.6 g of dicyclohexylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.42 g of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-bis (hydroxymethyl) butane in a 50 mL sample bottle 0.28 g of acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.9 g of Kuraray polyol P-1020 (trade name, manufactured by Kuraray Co., Ltd.) were added. To this was added 15.7 g of a 15 mass% heptane solution of polyurea colloidal particles Aa-1, and the mixture was dispersed with a homogenizer for 30 minutes while heating at 50 ° C. During this time, the mixture became fine particles and became a light orange slurry. The obtained slurry was put into a 100 mL three-necked flask heated to a temperature of 80 ° C. in advance, 0.1 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added, and the temperature was 80 ° C. and the rotation speed was 400 rpm. Stir for hours. The slurry became a white emulsion. Thereby, it was estimated that the polyurethane particle was formed. The white emulsion slurry was cooled to obtain a 40 mass% heptane dispersion of polyurethane particles (Binder B-3).

(Example 1)
<Preparation of solid electrolyte composition>
(1) Preparation of Solid Electrolyte Composition S-1 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, and LLZ (Li ₇ La ₃ Zr ₂ O ₁₂ , average particle size 5. 06 μm, manufactured by Toshima Seisakusho): 4.45 g, prepared amorphous oxide-based inorganic solid electrolyte LBO: 0.5 g, synthesized binder B-1: 0.05 g (solid content mass), heptane as dispersion medium : 17.0 g was charged. Thereafter, this container was set on a planetary ball mill P-7 manufactured by Fritsch, and mixing was continued at a temperature of 25 ° C. and a rotation speed of 300 rpm for 1 hour to prepare a solid electrolyte composition S-1.

(2) Preparation of solid electrolyte compositions S-2 to S-11 and T-1 Solid electrolyte composition S was prepared except that the composition was changed as shown in Table 1 in the preparation of solid electrolyte composition S-1. In the same manner as -1, solid electrolyte compositions S-2 to S-11 and T-1 were prepared.

<Measurement method>
-Measurement of solid content of binder-
10 g of the prepared binder dispersion was weighed on an aluminum cup, dried on a hot plate at 140 ° C. for 6 hours, and then the mass excluding the mass of the aluminum cup was measured. The ratio of the mass excluding the mass of the aluminum cup to the initially weighed 10 g was defined as the solid content concentration.

-Measurement of volume average particle size of binder-
A 1% by weight dispersion was diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used for preparation of the solid electrolyte composition, for example, heptane). The diluted dispersion sample was irradiated with 1 kHz ultrasonic waves for 10 minutes and used for the test immediately after that. Using this dispersion liquid sample, using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA), data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., The volume average particle diameter was measured. Five samples were prepared for each level and measured, and the average value was adopted.

-Measurement of molecular weight-
As the molecular weight of the binder used in the present invention, a mass average molecular weight in terms of standard polystyrene was adopted by gel permeation chromatography (GPC). The measurement apparatus and measurement conditions were based on the following condition 2 and were set to condition 1 depending on the solubility of the sample. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for the carrier were selected as appropriate.
(Condition 1)
Two columns: TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) were connected.
Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (Condition 2)
Column: TOSOH TSKgel Super HZM-H,
TOSOH TSKgel Super HZ4000,
TOSOH TSKgel Super HZ2000 (both trade names, manufactured by Tosoh Corporation)
A column connected with was used.
Carrier: Tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

<Table notes>
LLT: Li _0.33 La _0.55 TiO ₃ (average particle size 3.25 μm, manufactured by Toshima Seisakusho, X> 95)
LLZ: Li ₇ La ₃ Zr ₂ O ₁₂ (average particle size 5.06 μm, manufactured by Toyoshima Seisakusho, X> 95)
LBO: Amorphous oxide-based inorganic solid electrolyte LBO prepared above, X <10
LBO-LSO: Amorphous oxide-based inorganic solid electrolyte LBO-LSO prepared above, X <10

LLT, LLZ, it obtains the scattered intensity _{I a} of scattering intensity _{I c} and amorphous portions of the LBO and LBO-LSO crystal portion was calculated X from the formula (1). The method of measuring the I _c and _{I a} are shown below.
The measurement was performed using CuKα rays with an X-ray diffractometer from a 2θ value of 5 ° to 70 ° with a step number of 0.1 °, a step time of 1 second, and a voltage of 55 kV and a current of 280 mA. The peak is separated into a crystal part having a sharp peak with a full width at half maximum of less than 2 ° and an amorphous part having a broad peak with a full width at half maximum of 2 ° or more. The peak area of the crystal part is I _c , and the peak area of the amorphous part is Measured as _Ia .

B-1 to B-3: Binders B-1 to B-3 synthesized above
-B-4: Asahi Kasei Corporation product name: Tuftec M1913 (carboxylic acid-modified hydrogenated styrene butadiene rubber)
-B-5: ARKEMA product name: KYNAR301F (polyvinylidene fluoride)
-"-" In the binder column means that no binder is added. Accordingly, the molecular weight column of the solid electrolyte composition to which no binder is added is also indicated by “−”.
-"-" In the particle size column means that the binder is dissolved in the dispersion medium and the particle size is not measured.

<Preparation of composition for electrode active material layer>
-Preparation of composition for positive electrode of all solid state secondary battery-
180 zirconia beads having a diameter of 5 mm are put into a 45 mL container (manufactured by Fritsch) made of zirconia, and 6 parts by mass of NMC (LiNi _0.33 Co _0.33 Mn _0.33 O ₂ ) as a positive electrode active material, the above solid electrolyte Composition S-1: 10 parts by mass and 9 parts by mass of the dispersion medium used in the solid electrolyte composition S-1 were added, mixed at a temperature of 25 ° C. and a rotation speed of 100 rpm for 10 minutes, and tested No. shown in Table 3 below. . 201 composition for positive electrode of all-solid-state secondary battery was prepared.
Test No. Except that the all-solid-state secondary battery positive electrode compositions 202 to 206 and c21 were changed to the components shown in Table 3 below and the dispersion media used in the corresponding solid electrolyte compositions, the above test Nos. It was prepared in the same manner as 201 of the all-solid secondary battery positive electrode composition.
In Table 3 below, the all-solid-state secondary battery positive electrode composition is described in the column of the positive electrode active material layer.

-Preparation of composition for negative electrode of all solid secondary battery-
180 zirconia beads having a diameter of 5 mm are placed in a 45 mL container (manufactured by Fritsch) made of zirconia, 5 parts by mass of graphite as a negative electrode active material, 10 parts by mass of the above solid electrolyte composition S-1, and 10% by mass of solid electrolyte composition S- 9 parts by weight of the dispersion medium used in No. 1 was added and mixed for 10 minutes at a temperature of 25 ° C. and a rotation speed of 100 rpm. 201 All-solid-state secondary battery negative electrode compositions were prepared.
Except for changing to the components shown in Table 3 below and the dispersion medium used in the corresponding solid electrolyte composition, the above test No. 3 was used. In the same manner as in the all-solid-state secondary battery negative electrode composition of No. 202-206 and c21 all-solid-state secondary battery negative electrode compositions were prepared.
In Table 3 below, all-solid-state secondary battery negative electrode compositions are listed in the row of negative electrode active material layers.

<Creating a sheet>
-Production of solid electrolyte sheet-
The solid electrolyte composition S-1 was applied onto an aluminum foil having a thickness of 20 μm by a baker type applicator (trade name SA-201, manufactured by Tester Sangyo Co., Ltd.), heated at 80 ° C. for 1 hour, and further heated at 120 ° C. for 1 hour. Heated for a period of time to dry the dispersion medium. Thereafter, using a heat press, the solid electrolyte layer was heated (120 ° C.) and pressurized (600 MPa, 1 minute) so as to have a predetermined density. 101 solid electrolyte sheet was obtained. The film thickness of the solid electrolyte layer was 50 μm.
Except that the solid electrolyte composition S-1 was changed to the solid electrolyte composition shown in Table 2 below, test no. In the same manner as the solid electrolyte sheet of No. 101, Test No. Solid electrolyte sheets of 102 to 111 and c11 were prepared.

-Preparation of an electrode sheet for an all-solid secondary battery (hereinafter referred to as an electrode sheet for an all-solid secondary battery) comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer-
Test No. prepared above. 201 composition for a secondary battery positive electrode was applied onto an aluminum foil having a thickness of 20 μm by the applicator and dried at 120 ° C. for 2 hours. Then, using a heat press machine, it heated (120 degreeC) and pressurized (600 MPa, 1 minute) so that it might become a predetermined density, and formed the positive electrode active material layer.
Next, the solid electrolyte composition S-1 was applied onto the positive electrode active material layer with the applicator, heated at 120 ° C. for 2 hours, and dried to form a solid electrolyte layer.
Thereafter, the test No. prepared above on the solid electrolyte layer. 201, an all-solid-state secondary battery negative electrode composition was applied, heated at 120 ° C. for 2 hours, and dried to form a negative electrode active material layer. Using a heat press machine, heating (120 ° C.) and pressurization (600 MPa, 1 minute) were performed to obtain a predetermined density, and an electrode sheet for an all-solid-state secondary battery was produced.

<Battery performance test>
About the produced said solid electrolyte sheet and the electrode sheet for all-solid-state secondary batteries, the test of binding property and ion conductivity was done. The results are shown in Tables 2 and 3 below.

-Preparation of sample for ion conductivity measurement-
(1) Test No. Preparation of cells for measuring ion conductivity for 101 to 111, c11 The solid electrolyte sheet 12 was cut into a disk shape having a diameter of 14.5 mm and placed in a coin case. An aluminum foil cut into a disk shape having a diameter of 15 mm was brought into contact with the solid electrolyte layer, a spacer and a washer were incorporated, and placed in a stainless steel 2032 type coin case 11. By closing the coin case, the ion conductivity measuring cell 13 shown in FIG. 2 was produced.
(2) Test No. 201-206, Production of c21 Ion Conductivity Measurement Cell The electrode sheet 12 for an all-solid-state secondary battery was cut into a disk shape having a diameter of 14.5 mm, and a stainless steel 2032 type coin case 11 incorporating a spacer and a washer was formed. The indium foil cut out to 15 mmφ was placed on the negative electrode active material layer. A stainless foil was further stacked thereon, and then the coin case 11 was closed to produce an ion conductivity measurement cell 13 shown in FIG.

-Measurement of ionic conductivity-
Ionic conductivity was measured using the cell for measuring ion conductivity. Specifically, AC impedance was measured in a constant temperature bath at 30 ° C. using a 1255B FREQUENCY RESPONSE ANALYZER (trade name) manufactured by SOLARTRON to a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz. Thus, the resistance in the film thickness direction of the sample was obtained and calculated by the following formula (1).
Ionic conductivity (mS / cm) =
1000 × sample film thickness (cm) / (resistance (Ω) × sample area (cm ² )) (1)

-Binding test-
A cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.) having a width of 12 mm and a length of 60 mm was attached to the solid electrolyte layer (length: 50 mm, width: 12 mm) of the solid electrolyte sheet, and peeled off by 50 mm at a speed of 10 mm / min. In that case, it evaluated by the area ratio of the sheet | seat part which peeled with respect to the area of the peeled-off cellotape. The measurement was performed 10 times, and an average of 8 measurement values excluding the maximum value and the minimum value was adopted. The average value was adopted using five samples for each test.
The electrode sheet for an all-solid-state secondary battery was tested in the same manner by attaching a cello tape so that the cellulosic tape was in contact with the negative electrode active material layer.

5: 0 to less than 5% 4: 5% to less than 15% 3: 15% to less than 30% 2: 30% to less than 60% 1: 60% or more

As apparent from Table 2, the test No. 1 was prepared using a solid electrolyte composition satisfying the provisions of the present invention. The solid electrolyte sheets 101 to 111 are excellent in ionic conductivity. Further, Test No. 1 in which a binder was included in the solid electrolyte composition. The solid electrolyte sheets 101 to 109 and 111 showed not only ionic conductivity but also good binding properties.
On the other hand, test No. which does not satisfy the regulations of the present invention. The solid electrolyte sheet of c11 had insufficient ionic conductivity and binding properties.

<Notes on the table>
NMC: LiNi _0.33 Co _0.33 Mn _0.33 O ₂ nickel manganese lithium cobaltate LCO: LiCoO ₂ lithium cobaltate LTO: Li ₄ Ti ₅ O ₁₂ lithium titanate (trade name “Enamite LT-106”, Ishihara Sangyo Co., Ltd.)

As is apparent from Table 3, test no. The all solid state secondary batteries 201 to 206 are excellent in ionic conductivity. Further, Test No. 1 in which a binder was included in the solid electrolyte composition. The all solid state secondary batteries 201 to 205 exhibited not only ionic conductivity but also good binding properties.
On the other hand, test No. which does not satisfy the regulations of the present invention. The all solid state secondary battery of c21 was insufficient in both ionic conductivity and binding properties.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims the priority based on Japanese Patent Application No. 2015-110579 for which it applied for a patent in Japan on May 29, 2015, and these are all referred to here for the content of this specification. As part of.

DESCRIPTION OF SYMBOLS 1 Negative electrode current collector 2 Negative electrode active material layer 3 Solid electrolyte layer 4 Positive electrode active material layer 5 Positive electrode current collector 6 Working part 10 All solid secondary battery 11 Coin case 12 Solid electrolyte sheet or electrode sheet 13 for all solid secondary battery Ion conductivity measurement cell

Claims (16)

1. A solid electrolyte composition comprising a crystalline oxide inorganic solid electrolyte and an amorphous oxide inorganic solid electrolyte, wherein the crystalline oxide inorganic solid electrolyte and the amorphous oxide inorganic solid electrolyte A solid electrolyte composition having a volume ratio of 70 to 99.8: 0.2 to 30.
2. The solid electrolyte composition according to claim 1, comprising at least one binder having at least one functional group selected from the following functional group group [a].
   Functional group [a]
   Carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, hydroxy group, sulfanyl group, isocyanato group, oxetanyl group, epoxy group, dicarboxylic anhydride group, silyl group
3. The ratio of the volume of the crystalline oxide inorganic solid electrolyte to the volume of the amorphous oxide inorganic solid electrolyte to the volume of the binder is 70 to 99.8: 0.1 to 29.9: 0.1 to The solid electrolyte composition according to claim 2, which is 29.9.
4. The solid electrolyte composition according to claim 2 or 3, wherein the resin constituting the binder is selected from the group consisting of a hydrocarbon resin, a fluorine-containing resin, an acrylic resin, polyurethane, polyamide, polyimide, polyether, polyester, and polycarbonate. .
5. The solid electrolyte composition according to any one of claims 2 to 4, wherein the functional group [a] is the following functional group [b].
   Functional group [b]
   Carboxy group, sulfo group, phosphoric acid group, phosphonic acid group, hydroxy group, dicarboxylic anhydride group, silyl group
6. The solid electrolyte composition according to any one of claims 2 to 5, wherein the resin constituting the binder is an acrylic resin or polyurethane.
7. The solid electrolyte composition according to any one of claims 2 to 6, wherein the binder is particles having an average particle size of 0.01 to 10 µm.
8. The solid electrolyte composition according to any one of claims 1 to 7, wherein the amorphous oxide-based inorganic solid electrolyte comprises a compound represented by the following formula (I).
   Li _{xc Byc} M ^cc _{zc Onc} formula (I)
   In the formula (I), M ^cc is at least one selected from the group consisting of C, S, Al, Si, P, Ga, Ge, In and Sn, and xc, yc, zc and nc have a composition ratio. 0 <xc ≦ 5, 0 <yc ≦ 1, 0 ≦ zc ≦ 1, and 0 <nc ≦ 6.
9. The solid electrolyte composition according to any one of claims 1 to 8, wherein the crystalline oxide inorganic solid electrolyte is selected from compounds of the following formulae.
   ・ Li _xa La _ya TiO ₃
   xa = 0.3 to 0.7, ya = 0.3 to 0.7
   Li _xb La _yb Zr _zb M ^bb _{mb Onb}
   5 ≦ xb ≦ 10, 1 ≦ yb ≦ 4, 1 ≦ zb ≦ 4, 0 ≦ mb ≦ 2, 5 ≦ nb ≦ 20
   M ^bb is at least one selected from the group consisting of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn. Li _3.5 Zn _0.25 GeO ₄
   ・ LiTi ₂ P ₃ O ₁₂
   Li _{1 + xh + yh} (Al, Ga) _xh (Ti, Ge) _2-xh Si _yh P _3-yh O ₁₂
   0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1
   ・ Li ₃ PO ₄
   ・ LiPON
   ・ LiPOD ¹
   D ¹ is Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
   At least one selected from the group consisting of Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au. LiA ¹ ON
   A ¹ is at least one selected from the group consisting of Si, B, Ge, Al, C, and Ga.
10. The solid electrolyte composition according to any one of claims 1 to 9, comprising a dispersion medium.
11. The solid electrolyte composition according to any one of claims 1 to 10, comprising an active material.
12. An electrode sheet for an all-solid-state secondary battery formed by applying the solid electrolyte composition according to any one of claims 1 to 11 onto a metal foil.
13. A method for producing an electrode sheet for an all-solid-state secondary battery, wherein the solid electrolyte composition according to any one of claims 1 to 11 is applied onto a metal foil to form a film.
14. The manufacturing method of the electrode sheet for all-solid-state secondary batteries of Claim 13 including a press process.
15. A method for producing an all-solid secondary battery, comprising producing an all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer through the production method according to claim 13 or 14.
16. An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer is crystallized. A solid electrolyte composition containing a crystalline oxide-based inorganic solid electrolyte and an amorphous oxide-based inorganic solid electrolyte, wherein the volume of the crystalline oxide-based inorganic solid electrolyte and the amorphous oxide-based inorganic solid electrolyte An all-solid-state secondary battery formed by applying a solid electrolyte composition having a volume ratio of 70 to 99.8: 0.2 to 30 as a layer.

Images